Substituted poly aralkyl alkylene poly



United States Patent SUBSTITUTED POLY ARALKYL ALKYLENE POLY AMINO POLY ACETIC ACIDS AND SALTS Frederick C. Berswortll, Verona, N. J.'

5 Claims. (Cl. 260-518) Matter enclosed in heavy brackets [II appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue. I

This invention relates to metal ion chelating comunds for use in aqueous solutions and has for its obect the provision of a metal ion chelating compound which is utilizable in acid as well as alkaline pH solutions.

A further 'object is to provide a bactericidally active metal ion sequestering agent.

Still another object is to provide a metal ion sequestering agent that is particularly effective toward poly-valent heavy metals and metals of the so-called transition group of metals consisting of copper, nickel, cobalt, and the like.

Other objects will be apparent as the invention more fully disclosed.

In accordance with these objects, I have discovered that substituted poly alkylene polyamine polyacet1c acids corresponding to the formula:

out-coon x x mt-coon car-coon x x XQR- N-alkylene -Nalkylane-NRQX where n=l, 2, 3, 4; X=hydrogen, alkyl, halogen, hydroxyl of alkoxyl; alkylene='ethylene, proplyene, trimethylene, and R is a (CH2)n group wherein n is a numeral of the group consisting of l to 5, are highly water soluble bactcricides and fungicides having a strong sequestering power for metal ions (particularly the transition metals) in aqueous solution. The alkali metal salts are the most powerful sequestering agents, but the amino acids themselves are reactive toward such metals as Cu, Co, Ni, etc., i. e., the metals are chelated in acid as well as alkaline solutions.

In general, the sequestering action with alkaline earth ions is relatively 'weaker compared to such reagents as ethylene diamine tetraacetic acid, and these compounds are less useful for simple water softening. However, their high affinity for the transition ,metals [render] renders them effective antioxidants in aqueous [solution] solutions, or in materials which are to be used in or with water such as for instance bar soap with which they are active to remove the Re. 23,905 Reissued Dec. 14, 1954 "ice highly compatible and perform multifune-[tional] lions i. e., are anti-oxidants over long period of storage, protect the soap against water ness when used and being germicidally and fungicidally active, tend to sterilize when used. They are excellent adducts to elastomers both synthetic and natural and act as plasticizers and accepters and inhibitors of detrimental metal ions. They are excellent as reclaiming agents for natural and synthetic rubber being soluble in such rubber products and vulcanization metal catalyst in nonionic form. The chelates themselves may be used to introduce a desired metal into the plastic mixture to act as inhibitors aligo dynamic catalyst when so activated by temperature or working pressure, etc. The compounds are especially useful as oil additives both per se and in the form of their chelates to either act as emulsant viscosity [control] controllers and/or as [aid] aids in lubrication or combustion. 0f the compounds specifically disclosed, it was found that the bactericidal and fungicidal activity was greatest when both halogen and hydroxyl groups were present on the aromatic ring. This and their varying solubility in water and [emulsion] emulsions makes them desirable adducts tometal working emulsion type of lubricants as [antibiotics] anti friction additives. The [aminel] ammonium base salts are more soluble in organic systems than are the alkali metal salts although the potassium salts show remarkable solubility in polar solvents.

EXAMPLE I Two moles of 4-hydroxy-2,6-dichlorobenzyl chloride are reacted with one mole of diethylene triamine in aqueous ethanol by the gradual addition of an ethanol solution of the halide to the amine; the reaction mixture being maintained at vigorous reflux. The addition is made over a period of 3-4 hours and the reaction is completed by reflux for an additional hour. The product is mairlijly (about the dihydrochloride of the followmg ase:

To obtain the free base of the compound, the reaction mixture is treated with 2 moles of sodium hydroxide and agitated-until all chloride ion isreacted to form sodium chloride. This is filtered off as it is precipitated and the final filtrate may be vacuum dried and the organic free base extracted with alcohol to obtain a product practically free from inorganic salt. The resulting diethylene triamine derivative is dissolved in anhydrous ethanol and is carboxymethylated in accordance with the carboxymethylation reaction described in my Patents Nos. 2,387,735, 2,407,645 and 2,461,519, using 3 moles of sodium cyanide and 3 moles of CHaO and maintaining alkaline conditions in the reaction solution. The carboxymethylation reaction proceeds smoothly with good agitation at a reaction temperature of about C. The resulting carboxymethylated product is the trisodium salt of di[2,4-dich1oro-]-(2,6-dichlor0)4-[hydroxy benzyl] hydroxybenzyD-diethylene triamine triacetic acid having the formula:

CHrCOOH (11 Cl C|3HrCOOH ([JHz-COOH E0 CHr-NCHrCHsN-CH:CHr-N-CH 0H CHnCOONa CHICOONa CHICOONU It may be obtained as the crystalline sodium salt by This substance is somewhat less water soluble than the c gq of 9 of the water and adding alcohol product of Example I but it is more surface active as well elem to'pmvlde' about a solsovalgohol'aquwus 801- as having the other desirable properties of the products of The free amino acid is obtained by acidification of the 5 this mvelmonreaction solution with a mineral acid (such as HCl), The polyalltylene polyamme bases employed in the evaporating y and Wm! Warm abwlute above examples are generally recognized by members of ethanol. The. purified amino acid may be isolated in crystalline form relatively free from inorganic salts by 86mm! class of p unds expressed by the formul evaporation of the alcohol extract. 10 Nnhfiflkyle ylene- EXAMPLE II where n is a small integer. The bases of this type in which I have found that (11 to ylene triamine may be substituted for diethylene t i'iar ine in Example I to give a n varies from one to four inclusive are well known and product having the formula: 15 the ethylene and propylene bases are readily available cut-coon c1 c1 CHs-COOH cut-c0011 no CHrNGH-OH:NCHOHr-N-OH OH 1 HI H: I l

The methyl group increases the solubility of the amino commercially. I have found that such polyethylene bases cid in or anic solvents. a I have fgund that the process of Example I may also be may be uscd as substamlal z f for those m the used to prepare similar chelating agents in which the suhexamples above, the products having in general the exstituents on the ring, the length of the chain (R) between pected mama I have found for example, hat the 1 th rin and the amino rou s; and the alk lene grou s at: varied. g p y P use of tetraethylene pentamme in place of diethylene tri- EXAM L I amine of Example I produces a similar bactericidal and Thu the 1186 Of P'hydmxybenzyl chloride. the hahde fungicidal chelating agent which is water soluble. Thus and di-trimethylene triamine far I have faded to obtain the ammo acid in pure form Ha-CH -CH 'CHa--NHCH CH -CHzNHz (N 2 2 2 2 40 although its alkali metal salt is a crystalline material.

as the base resulted in the formation of an analogous amino acid which must have the formula: This is probably due to impurities resulting from side CHs-COOH CHs-COOH GHrCOOH The water solubility of this compound and its metal reactions in the substitution of the polyalkylene polygggsfi ggf gg i 5 :55? g d fi fg amine with the alkyl halide to give some substitution on this substance is a useful intermediate for the further 55 the Secondary flitl'ogells 0f the p y The Product,

substitution of halogenin the aromatic ring, to give from howgver was a p w f l chelating agent and contained 1 to 4 halogens in the various positions. When two halofivg acetic acid on s afte carbox 6th 1 It gens are introduced It is believed that they are attached p ym y a at the positions marked by X. believed that a large proportion of the reaction product X GHrGOOH x GHz-COOH CHz-COOH consists of the analogous compound having the formula:

EXAMPLEIV urn-coon v 01 01 Similarly, the process of Example I was found satiscmcoon factory for the synthesis from p-chlorophenylpenthyl- 7 H0 CHr N-CHrCHi N-CH 0H t chloride and diethylene triamine' of the amino acid hav- 1 ing the formula: 1

The reaction of the dialkylene triamine chelates was Hs-OOOH cat-coon (JHI'COOH 6 found to involve a 1:1 combination of heavy metal to ene is one of the group consisting of CH2.CH2, chdms having Emma CH2.CH2.CH: and cmcrnycm; x is one of the group X x E X x consisting of hydrogen, alkyl, alkoxyl, hydroxyl and halo- Q gen with one to three X being halogen, and n [is a x C I x numeral selected from the group consisting of 1 to 4-] C00 000 is an integer having a value in the range from 1 to 4, X CH|CO0Me x x and the alkali metal and ammonium base salts of the x R- nlkyleneN-nlk lneN-R 1: said compounds.

PM" 0 1B} 2. The compound conforming the the structural $00 00 formula: This accounts for the sequestering action of the amino CHs-COOH 01 Cl CHrCOOH CHrCOOH HO CHr-l-CEIrCHr-bF-CHIrU-Hr-N-CH OH acid for divalent metal ions, and the free saltforming 3. The compound conforming to the structural acetic acid group apparently accounts for the solubility formula:

. Uni-COOK CHrCOOH CHr-COOH KOO-CHs-fii-CflrCHrCHs-IlF-CHx-CHs-CHr-ILI-Cflr-OOH of the metal [chelate] chelates in water. 4. The compound conforming to the structural l have also found that the compounds of the present formula:

OlO(CK:)gN-CH1-GHr-NCflr CH1N(CH:) c1

om-coon (nu-coon din-coon invention which are derived from the higher polyalkylene 5. The compound conforming to the structural polyamines sequester more than one mole of metal per rm mole of chelating agent. For example, it was found that Cl CHI'COOH CHB'COOH a single disubstitutcd triethylene tetraamine tetraacetic 'acid combined with two moles of copper ions to give HO CH:

an inner complex salt presumably having the following x x x x x BN-clkylene-N-clkylene-Nclkylene-N-RQX x n. ctr on. JJRcu cm X X X X X R-N--allfleae-N-allfleae-Ndt7leae-N-R X RC8 He lHe 00 He Although the structure given here shows 7 that all salt References Cited in the tile of this patent forming (solubihzmg) groups are neutralized, forming or the original patent non-ionic chelate, they do not precipitate in alkaline solutron. It appears that secondary salt formation occurs, UNITE S A S PATENTS probably a phenolate. Number Name Date Having hereinabove described the present invention 868 294 Schmidlin Oct 15 1907 generically and specifically and given several specific cx- 932266 Fussene 1909 amples of the same by way of illustration but not by way 2 195'974 Re e fi 1940 of limitation, it IS believed apparent that the invention 7" 2'489'363 fg "fi 1949 may be widely varied without essential departure there- 2539'212 Strobcl at 1951 from and all suchlmoiiifications and adaptations of the same are contem ate as ma fall within the sco e o the following claims: y p FOREIGN PATENTS What is claimed is: Number Country Date 1. The compound conforming to the structural 18.095 Great Britain of 1913 formula: 642,244 Germany Mar. 6, 1937 x x OKs-COOK OHs-COOH OHaCOOH I X wherein z is [a numeral of the group consisting of l to 5] OTHER REFERENCES an integer having a value in the range from 1 to 5; alkyl- Alphen: Chem. Abs., vol. 38, col. 4943 (1944). 

